1-amino-4-hydroxy-2-(alkylthio-and hydroxyalkylthiophenoxy)-anthraquinones



United States Patent C F 3,293,270 1 AMINO 4 HYDROXY 2 (ALKYLTHIO- AND HYDROXYALKYLTHIOPHENOXY) ANTHRA- QUINONES Volker Hederich, Cologne-Deutz, Gunter Gehrke, Cologne-Flittard, and Karlfried Wedemeyer, Cologne- Stammheim, Germany, assignors to Farbeufabriken Bayer Aktiengesellschaft, Leverknsen, Germany, a corporation of Germany N Drawing. Continuation of application Ser. No. 245,419, Dec. 18, 1962. This application Sept. 27, 1965, Ser. No. 490,678 Claims priority, application Germany, Dec. 23, 1961, F 35,650 8 Claims. (Cl. 260-380) The present case is acontinu-ation of Serial No. 245,419, filed on December 18, 1962, and now abandoned.

This case relates to new anthraquinone dyestuffs.

It has been found that valuable anthraquinone dyestuffs for synthetic fibers areobtained by reacting l-amino- 2-halo-4-hydroxy-anthraquinone with optionally substituted alkyllmercapto phenols.

The dyestuffs obtained according to the invention may be represented by the following formula:

wherein R stands for an alkyl or hydroxy alkyl radical, X means alkyl, alkoxy or hydroxy alkoxy radicals and n represents a Whole number from 0 to 3.

The alkylmercapto phenols can contain as alkyl radicals preferably lower alkyl radicals, for example with up to 6 carbon atoms, and which may also contain hydroxy groups. The alkyllmercapto phenols may also contain in the aromatic part further substituents, such as for example alkyl groups, preferably alkyl groups with up to 4 carbon atoms, allcoxy or hydroxy alkoxy groups, the alkyl groups being again preferably lower alkyl groups. Examples of such compounds are as follows: 2- or 3- or 4 rnethyl mercaptophenol, 2- or 3- or 4-ethylmercapto phenol, 2- or 3- or 4-(2'-hydroxy ethyl-mercapto)-phenol, 4-me-thyl mercapto-S-methyl phenol, 4-methylmercapto-3,S-dirnethyl phenol, or 4-methylmercapto-Z-methoxy phenol.

The reaction of the 1-amino-2-halo-4-hydroxy-anthraquinones, preferably of the technically obtainable l-amino- 2-bromoor -ch-loro-4-hydroxy-anthraquinone, with the alkyl mercapto phenols is carried out in a manner known as such in the presence of strongly alkaline compounds, such as for example potassium or sodium hydroxide or carbonate. The reaction is advantageously carried out in an excess of the alkyl mercapto phenol at temperatures from 100l80 C.

The new dyestuffs can chiefly be used as dispersion dyestuffs for synthetic fibers, preferably of linear polyesters. They can be dyed according to the methods usual for these fibers, for example at 1l0130 C. under pressure or at boiling temperature in the presence of so-called carriers, for example chloro benzene, 2- or 4-hydroxy diphenyl, salicyclic acid or -methyl esters. The new dyestufis can also be applied in mixtures with one another and are with advantage, finely dispersed by the usual methods in the presence of dispersing agents, if desired.

On linear polyester fibers the new dyestuffs produce red dyeings with very good fastness properties, especially good resistance to dry heat treatment such as resistance to sublimation and thermofixation.

The following examples are given for the purpose of illustrating the invention. The parts given'are parts by weight.

Example 1 100 parts of technical 4-methylmercapto-3-methyl phenol are heated to 100 C. with 10 parts of anhydrous potassium carbonate, 20 parts of l-amino-2-bromo-4-hydroxy-anthraquinone are introduced into the melt whilst stirring, and the mixture is heated at 150 C. six hours. After termiantion of the reaction, the reaction mixture is cooled to C. and diluted with 100 parts of methanol. The precipitated red dyestufi is filtered off with suction, washed with hot Water and dried at C.

The yield of crude product is nearly quantitative. From chlorobenzene the dyestufi crystallises as red needles of melting point 225227 C.

1 part of this dyestuif which has previously been finely divided in the presence of dispersing agents is dispersed in 3000 parts of Water. In the dyebath thus obtained parts of polyester fabric, for example polyethylene glycol terephthalate, are dyed at C. for one hour. A brilliant red dyeing is obtained of very good fastnes-s to light and excellent fastness to sublimation.

Example 2 Into a melt of 50 parts of 4-methylmercapto-phenol and 10 parts anhydrous potassium carbonate, 20 parts of lamino-2bro-n1o-4-hydroxy-anthraquinone are introduced. After heating at l40150 C. for 4-5 hours the reaction is completed. The reaction mixture, cooled to 8090 C., is diluted With 50 parts of methanol. After suctionfiltration, washing with methanol and hot water the resultant dyestufi is dried at 90 C. 20.2 parts of crude product are obtained which crystallises from chlorotoluene in the form of red darts. The melting point is 170 C.

With 1 part of this dyestufi" in a finely dispersed form 100 parts of polyester fibers, for example polyethylene glycol terephthalate, are dyed for 120 minutes at boiling temperature in 4000 parts of water in the presence of 15 parts of o-cresotic acid methylester as carrier. A clear red dyeing of very good fastness to light and subliming is obtained.

Example 3 12 parts of l-amino-2-bromo-4-hydroxy-anthraquinone are introduced into a melt at 120 C. consisting of 70 parts of 4-rnethylmercapto-3,5-dimethyl-phenol and 6 parts of anhydrous potassium carbonate. The reaction mixture is heated at C. for 7 hours, subsequently cooled to 90 C. and treated with 50 parts of methanol. The red dyestulf is filtered off with suction, washed with methanol and hot water, and dried at 90 C. The yield of crude product amounts to 14.1 parts. The crude product is re-crystallised from chlorobenzene or chlorotoluene and melts at 2142l5 C. On polyester fabric, for example polyethylene glycol terephthalate, the dyestutf obtained produces a clear bluish red shade of very good fastness properties.

Example 4 4 parts of l-amino-2-br0rno-4-hydroxy-anthraquinone are introduced into a melt of 30 parts of 4-methylmercapto-3-methylphenol and 3 parts of powdered potassium hydroxide. After heating at 175 C. for 1 /2 hours the reaction is completed. The reaction mixture is cooled to 100 C., treated with 200 ml. of a 25% sodium carbonate solution, then boiled for a short time, filtered off with suction while hot and carefully washed with hot water.

3.8 parts of crude dyestuff are obtained which is identi cal with the reaction product obtained according to Ex ample l.

ene, melts at 169-170 C.

- Example 5 3. A compound of the formula From 22 parts of Z-methylmercaptophenol and 4 parts NH, CH of anhydrous potassium carbonate a melt is prepared into N l which at about 120 C. 7 parts of l-amino-2-bromo-4-hyo--sclh droxyanthraquinone are introduced. After heating at 160 l C. for 5 hours the reaction is completed. Working up is carried out as indicated in Example 1. 6.2 parts of dye- Y stuff are obtained which, after re-crystallisation from tolu- 0 OH 4. A compound of the formula Example 6 According to the method given in Example 1, parts T (3H3 of 4-ethyl-mercapto-phenol, 4 parts of anhydrous potas- A sium carbonate and 8 parts of 1-amino-2-bromo-4-hydroxy-anthraquinone are reacted. 8.7 parts of dyestufi 5 l I I are obtained which, after recrystallisation from chlorotol- Y CH3 uene, melts at 175-158 C. On polyester fabric, for ex- I ample polyethylene glycol terephthalate, the dyestufi O OH yields a brilliant red shade of very good fastness proper- 2 A compound of the formula ties. 0

Example 7 f? OOHa 35 parts of 4-methylmercapto-2-methoxy-phenol, 4 o SCH parts of anhydrous potassium carbonate and 8 parts of 1- amino-2-bromo-4-hydroXy-anthraquinone are reacted at 25 150 C. as described in Example 1, and yield 8 parts of I red dyestuff which, after re-crystallising from chlorotol- 0 0H uene, melts at 195-196 C., and produces on polyester fabric, for example polyethylene glycol terephthalate, a A compound of tha fmmula clear red shade of very good fastness properties. 0

Example 8 I NHa From 25 parts of 4-(2'-hydroxyethylmercapto)-phenol Q and 2.6 parts of anhydrous potassium carbonate a melt is I prepared at 100 C. under a nitrogen atmosphere. After i SCH:

the addition of 8 parts of 1-amino-2-bromo-4-hydroxy-an- Y thraquinone the reaction takes place at 150 C. within 2 0 hours. After cooling, the reaction mixture is treated With A Compound of the formula 20 parts of methanol and filtered off with suction after standing for several hours. After washing with a warm 0 NH: dilute sodium carbonate solution and drying at 80 C., 7.4 parts of a red dyestuif are obtained which, after re-crys- OQ-S-Czlia tallisation from chlorotoluene, melts at 189-191 C. and produces on polyester fabric, for example polyethylene glycol terephthalate, a clear red shade of very good fast- H ness properties. 0 OH We claim:

1. A compound of the formula OH OH wherein R is a member selected from the group consisting References Cited by the Examiner of lower alkyl and hydroxy lower alkyl; X is a member selected from the group consisting of lower alkyl and UNITED STATES PATENTS lower alkmyiand 0f 2,072,259 3/1937 Haddock et al. 260380 X 2. A compound of the formula 0 OTHER REFERENCES NH: German Auslegeschrift (Maier), 1,113,051, August I o-sorn 1961 3 pp. spec.). LORRAINE A. WEINBERGER, Primary Examiner,

Q or! H. C. WEGNER, Assistant Examiner. 

1.A COMPOUND OF THE FORMULA 